Sustainable catalysis : challenges and practices for the pharmaceutical and fine chemical industries / edited by Peter J. Dunn ... [et al.].

Format:

Book

Contributor:

Dunn, Peter J. (Peter James)

Language:

English

Subjects (All):

Green chemistry.

Chemical engineering.

Catalysts.

Pharmaceutical industry--Waste minimization.

Pharmaceutical industry.

Physical Description:

xv, 421 p. : ill.

Edition:

1st ed.

Place of Publication:

Hoboken, N.J. : Wiley, 2013.

Summary:

Opens the door to the sustainable production of pharmaceuticals and fine chemicals Driven by both public demand and government regulations, pharmaceutical and fine chemical manufacturers are increasingly seeking to replace stoichiometric reagents used in synthetic transformations with catalytic routes in order to develop greener, safer, and more cost-effective chemical processes. This book supports the discovery, development, and implementation of new catalytic methodologies on a process scale, opening the door to the sustainable production of pharmaceuticals and fine chemicals. Pairing contributions from leading academic and industrial researchers, Sustainable Catalysis focuses on key areas that are particularly important for the fine chemical and pharmaceutical industries, including chemo-, bio-, and organo-catalytic approaches to C-H, C-N, and C-C bond-forming reactions. Chapters include academic overviews of current innovations and industrial case studies at the process scale, providing new insights into green catalytic methodologies from proof-of-concept to their applications in the synthesis of target organic molecules. Sustainable Catalysis provides the foundation needed to develop sustainable green synthetic procedures, with coverage of such emerging topics as: * Catalytic reduction of amides avoiding LiAlH4 or B2H6 * Synthesis of chiral amines using transaminases * Industrial applications of boric acid and boronic acid catalyzed direct amidation reactions * C-H activation of heteroaromatics * Organocatalysis for asymmetric synthesis Offering a balanced perspective on current limitations, challenges, and solutions, Sustainable Catalysis is recommended for synthetic organic chemists seeking to develop new methodologies and for industrial chemists dedicated to large-scale process development.

Contents:

SUSTAINABLE CATALYSIS: Challenges and Practices for the Pharmaceutical and Fine Chemical Industries

Contents

Foreword

Preface

Contributors

Abbreviations

1 Catalytic Reduction of Amides Avoiding LiAlH4 or B2H6

1.1 INTRODUCTION

1.2 AMIDES

1.3 IMPORTANCE OF AMIDE REDUCTIONS IN PHARMACEUTICAL SYNTHESIS

1.4 HETEROGENEOUS AMIDE HYDROGENATION

1.5 HOMOGENEOUS AMIDE HYDROGENATION

1.5.1 Hydrogenation of Primary Amides

1.5.2 Hydrogenation of Secondary Amides

1.5.3 Tertiary Amides

1.5.4 Scope of Ru/Triphos Amide Hydrogenation

1.5.5 Hydrogenation of Diacids in the Presence of Amines

1.5.6 Homogeneous Amide Hydrogenation Mechanism

1.5.7 Amide C - N Cleavage by Hydrogenation

1.6 HYDROSILATION

1.6.1 Rhodium-Catalyzed Reduction of Amides Using Silanes

1.6.2 Ruthenium-Catalyzed Reduction of Amides Using Silanes

1.6.3 Platinum-Catalyzed Reduction of Amides Using Silanes

1.6.4 Molybdenum-Catalyzed Reduction of Amides Using Silanes

1.6.5 Indium Bromide-Catalyzed Reduction of Amides Using Silanes

1.6.6 Iron-Catalyzed Reduction of Amides Using Silanes

1.6.7 Zinc-Catalyzed Reduction of Amides Using Silanes

1.7 CONCLUSIONS AND FUTURE PERSPECTIVES

REFERENCES

2 Hydrogenation of Esters

2.1 INTRODUCTION

2.2 HYDROGENATION OF ALIPHATIC ESTERS

2.3 HYDROGENATION OF LACTONES

2.4 HYDROGENATION OF AROMATIC ESTERS

2.5 HYDROGENATION OF FURANOIC ESTERS

2.6 HYDROGENATION OF CHIRAL ESTERS (BASE-FREE CONDITIONS)

2.7 CONCLUSIONS

3 Synthesis of Chiral Amines Using Transaminases

3.1 IMPORTANCE OF CHIRAL AMINES

3.1.1 Challenges with Chemocatalytic Synthesis of Chiral Amines

3.2 TRANSAMINASES

3.2.1 Transaminase Mechanism

3.2.2 Transaminase Selectivity

3.3 TRANSAMINASE-CATALYZED RESOLUTION OF RACEMIC AMINES.

3.4 TRANSAMINASE-CATALYZED ASYMMETRIC SYNTHESIS OF AMINES

3.5 CONCLUSIONS

4 Development of a Sitagliptin Transaminase

4.1 INTRODUCTION

4.2 CREATING ACTIVITY

4.3 TRANSAMINASE EVOLUTION

4.4 PROCESS OPTIMIZATION

4.5 A GENERAL AMINATION METHODOLOGY

4.6 CONCLUSION AND OUTLOOK

4.7 PROCEDURES

4.7.1 Transaminase Reaction at 1 kg Reaction Scale

4.7.2 FiltrationWorkup

4.7.3 Direct Extraction Workup

5 Direct Amide Formation Avoiding Poor Atom Economy Reagents

5.1 INTRODUCTION

5.2 MECHANISM FOR BORONIC AND BORIC ACID CATALYSIS

5.3 BORIC ACID-BASED CATALYSIS

5.4 BORONIC ACID-BASED CATALYSIS

5.5 TRIAZINE-BASED REAGENTS

5.6 TITANIUM(IV)-BASED REAGENTS

5.7 ANTIMONY-BASED REAGENTS

5.8 HETEROGENEOUS CATALYSTS AND MICROWAVE-ASSISTED AMIDE SYNTHESIS

5.9 SUMMARY AND FUTURE DIRECTIONS

6 Industrial Applications of Boric Acid and Boronic Acid-Catalyzed Direct Amidation Reactions

6.1 INTRODUCTION

6.2 THE SYNTHESIS OF EFAPROXIRAL UTILIZING A DIRECT AMIDATION REACTION

6.3 DIRECT AMIDATION EXAMPLES FROM DR. REDDY'S LABORATORIES

6.4 DIRECT AMIDATION EXAMPLES FROM PFIZER

6.5 POTENTIAL TOXICITY OF BORIC ACID

6.6 CONCLUSIONS

ACKNOWLEDGMENT

7 OH Activation for Nucleophilic Substitution

7.1 INTRODUCTION

7.2 FORMATION OF C - C BONDS FROM ALCOHOLS

7.3 FORMATION OF C - N BONDS FROM ALCOHOLS

8 Application of a Redox-Neutral Alcohol Amination in the Kilogram-Scale Synthesis of a GlyT1 Inhibitor

8.1 INTRODUCTION

8.2 BACKGROUND AND INITIAL SYNTHETIC WORK

8.3 FIRST-GENERATION SYNTHESIS OF 10

8.4 FIRST APPLICATION OF IR CHEMISTRY AND INITIAL PROCESS DEVELOPMENT EFFORTS

8.5 PROCESS OPTIMIZATION OF THE AMINATION REACTION

8.5.1 Reliability Optimization

8.5.2 Catalyst Loading Optimization.

8.5.3 Solvent Optimization and Additional Parameters

8.5.4 Kilogram-Scale Runs under Optimized Conditions

8.6 MECHANISTIC DISCUSSION

8.7 IRIDIUM CONTROL

8.8 FINAL COMMENTS

ACKNOWLEDGMENTS

9 Olefin Metathesis: From Academic Concepts to Commercial Catalysts

9.1 INTRODUCTION

9.2 RECOVERY AND REUSE OF RU-BASED METATHESIS CATALYSTS: THE ACADEMICS' VIEW

9.3 APPLICATION OF RUTHENIUM METATHESIS CATALYSTS IN WATER

9.4 SUMMARY AND OUTLOOK

10 Challenge and Opportunity in Scaling-up Metathesis Reaction: Synthesis of Ciluprevir (BILN 2061)

10.1 INTRODUCTION

10.2 SYNTHESIS OF CILUPREVIR (BILN 2061) AND CRITICAL CHALLENGES

10.3 PREPARATIONS OF BUILDING BLOCKS

10.4 THE FIRST GENERATION CILUPREVIR (BILN 2061) PROCESS

10.5 CHALLENGES IN SCALING UP THE RCM REACTION

10.6 DEVELOPMENT OF A PRACTICAL AND SCALABLE RCM PROCESS

10.7 THE SECOND GENERATION CILUPREVIR (BILN 2061) PROCESS

10.8 CONCLUSION

11 C-H Activation of Heteroaromatics

11.1 INTRODUCTION

11.2 DIRECT ARYLATION

11.2.1 C - H/ C - X Coupling

11.2.2 C - H /C - M Coupling

11.2.3 C - H/C - H Coupling

11.3 DIRECT ALKENYLATION

11.3.1 Coupling with Alkenyl Halides

11.3.2 Coupling with Alkenes (Fujiwara - Moritani Reaction)

11.3.3 Coupling with Alkynes (Hydroarylation)

11.4 DIRECT ALKYNYLATION

11.4.1 Coupling with Alkynyl Halides or Pseudohalides

11.4.2 Coupling with Terminal Alkynes

11.5 DIRECT ALKYLATION

11.5.1 Benzylation and Allylation

11.5.2 Alkylation with Unactivated Systems

11.6 CONCLUSION

12 The Discovery of a New Pd/Cu Catalytic System for C-H Arylation and Its Applications in a Pharmaceutical Process

12.1 INTRODUCTION

12.2 DEVELOPMENT OF INITIAL PROCESS FOR THE AGONIST OF S1P1.

12.3 DEVELOPMENT OF C - H ARYLATION FOR THE SYNTHESIS OF AMG 369

12.3.1 Initial Results

12.3.2 Discovery of a New Cocatalyst

12.3.3 Applications to the Synthesis of AMG 369

12.3.4 Latest Developments and Future Perspective

12.4 CONCLUSION

13 Diarylprolinol Silyl Ethers: Development and Application as Organocatalysts

13.1 INTRODUCTION AND BACKGROUND

13.2 ENAMINE INTERMEDIATE

13.2.1 Michael Reaction

13.2.2 Acetaldehyde as Nucleophile

13.2.3 a-Oxidation Using Benzoyl Peroxide

13.2.4 Tandem Reaction Between Nitro-olefin and Pentane-1,5-dial

13.2.5 Multicomponent Reactions

13.2.6 [6+2] Cycloaddition

13.3 IMINIUM ION INTERMEDIATE

13.3.1 Diels-Alder and Ene-Type Reactions of Cyclopentadiene

13.3.2 Nitroalkane as a Nucleophile

13.3.3 Nitroethanol as Nucleophile

13.3.4 Formal Aza- and Carbo-[3+3] Cycloaddition

13.4 FORMAL C - H INSERTION

13.5 REACTIONS IN THE PRESENCE OFWATER

13.6 SYNTHESIS OF BIOLOGICALLY ACTIVE MOLECULES

13.6.1 Synthesis of ( - )-b-Santalol

13.6.2 Synthesis of Oseltamivir

13.6.3 Synthesis of ABT-341 (127)

13.7 CONCLUSION

14 Organocatalysis for Asymmetric Synthesis: From Lab to Factory

14.1 INTRODUCTION

14.2 PREPARATION OF TELCAGEPANT, AN APPLICATION OF IMINIUM ORGANOCATALYSIS

14.2.1 Background and Synthetic Strategy

14.2.2 Preliminary Results, Identification of By-products, and Reaction Pathway Consideration

14.2.3 "Cocktail" Cocatalysts in Non-alcohol Solvents

14.2.4 The Use of Crude Jørgensen - Hayashi Catalyst

14.2.5 Evolution to a Streamlined Through-process

14.2.6 Completion of Telcagepant Synthesis

14.3 PREPARATION OF MK-8613, APPLICATION OF ASYMMETRIC MICHAEL ADDITION CATALYZED BY DESMETHYL QUINIDINE

14.3.1 Synthetic Target and Strategy Analysis.

14.3.2 A Practical Process to Prepare Catalyst DMQ

14.3.3 Substrate-Specific Process Evolution

14.3.4 Completion of MK-8613 Synthesis

14.4 CONCLUSIONS

15 Catalytic Variants of Phosphine Oxide-Mediated Organic Transformations

15.1 GENERAL INTRODUCTION

15.2 WITTIG CHEMISTRY

15.3 AZA-WITTIG CHEMISTRY

15.4 MITSUNOBU CHEMISTRY

15.5 APPEL HALOGENATIONS

15.6 CONCLUSIONS

16 Formation of C-C Bonds Via Catalytic Hydrogenation and Transfer Hydrogenation

16.1 INTRODUCTION: MINIMIZING PREACTIVATION FOR SYNTHETIC EFFICIENCY

16.2 CARBONYL AND IMINE VINYLATION

16.3 CARBONYL ALLYLATION AND PROPARGYLATION

16.4 ALDOL, MANNICH, AND RELATED PROCESSES

16.5 FUTURE DIRECTIONS

Index.

Notes:

Includes index.

Includes bibliographical references and index.

ISBN:

9781523111060

1523111062

9781299402485

1299402488

9781118354520

1118354524

9781118354506

1118354508

9781118354513

1118354516

OCLC:

821560868